Production of halocycloalkanes



Patented Sept. 6, l 949 OFFICE PRODUCTION or HALocrcLoALKANEs Louis Schmerling,

Riverside, Ill., assignor to Universal i! Products Company, corporation of Delaware Chicago, Ill., a

No Drawing. Application November 28, 1947,

Serial No.

22 Claims.

This application is a continuation-in-part of my co-pending application Serial No. 496,617 filed July 29, 1943 and co-pending application Serial No. 496,951 filed July 31, 1943, both now abandoned.

This invention relates to the production of a halocycloalkane. More particularly the process relates to the addition of a monohalocycloparafiin to an unsaturated compound selected from the group consisting of a monoolefin and a halomonoolefin in the presence of a catalyst to produce a higher boiling halocycloparafiin with a molecular weight equal to the sum of molecular Weights of the halocycloalkane and unsaturated compound charged to the process.

The process is concerned with a catalytic method of adding to or condensing with a monoolefin or halomonoolefin, a ch1oro-, bromo-., or iodocycloalkane and particularly a monochloro-, monobromo-, or monoiodocycloalkane.

In this specification, the term condensing is used in referring to the process of chemically combining a monohalocycloalkane with a monoolefinic compound selected from the group consisting of a monoolefin and a halomonoolefin preferably a monohalomonoolefin to form a halocycloalkane with higher boiling point and with a molecular weight equal to the sum of the molecular weights of the reacting halocycloalkane and unsaturated compound. The condensation reaction may also be regarded as an addition of the monohalocycloalkane to the olefinic compound. The condensation may include the reaction of the monohalocycloalkane with more than one molecular proportion of the monoolefin or haloolefin; that is, the product of condensation of one mole of each of the halocycloalkane and olefin or haloolefin may react with a second, third, etc. mole of the unsaturated compound to form a halocycloalkan-e of higher molecular weight.

An object of this invention is to provide a process for manufacturing a halocycloalkane.

Another object of this invention is to provide a process for condensing in the presence of a Friedel-Crafts catalyst a monohalocycloalkane and a monoolefin.

A further object of this invention is to provide a process for condensing a monohaloolefin and a monohalocycloalkane each containing a halogen atom with an atomic weight of from about 35 to about 80 in the presence of a metal halide catalyst.

One specific embodiment of this invention relates to a process for producinga higher boiling halocycloalkane which comprises chemically combining in the presence of a Friedel-Crafts metal halide catalyst a monohalocycloalkane and a monoolefinic compound selected from the members of the group consisting of a monoolefin and a halomonoolefin.

,Another embodiment of this invention relates to a process for producing a higher boiling chlo- IOCYCIOELIKQIIB which comprises chemically combining in the presence ofa Friedel-Crafts catalyst, a monochlorocycloalkane and a monoolefinic compound selected from the members of the group consisting of a monoolefin and a halomonoolefin.

Halocycloalkanes which may also be referred to as halocycloparaflins and as halonaphthenes include halocyclopentanes, halocyclohexanes, halodecalins and other halogenated saturated cyclic compounds. The halogenated naphthenes and particularly the. chloronaphthenes may be obtained from any suitable source. More speoific examples of suitable halonaphthenes include tertiary monohalocycloalkanes such as l-chlorol-methylcyclopentane, l-chloro-l-methylcyclohexane, l-chloro-l-ethylcyclohexane, and 9- chlorodecahydronaphthalene and secondary monohalocycloalkanes as chlorocycloalkane and bromocycloalkane. The first two compounds may be prepared from the corresponding alcohols which may be synthesized by reaction of methylmagnesium chloride on cyclopentanone and cyclohexanone, respectively. The abovementioned chlorodecalin may be obtained by the addition of hydrogen chloride to 9,10-octa1in.

Another method for making tertiary halocycloparafiins consists in adding a hydrogen halide to the double bond of a cyclo-olefin in which one of the hydrogen atoms attached to the double bonded carbon atoms is substituted by an alkyl group. For example, the addition of hydrogen chloride to 1-methy1cyclohexene-l produces 1- chloro-l-methylcyclohexane.

Secondary halocycloparafiins may be prepared either from the appropriate alcohol or by the addition of hydrogen halide to the appropriate cycloolefin.

Halocycloparafiins which I prefer to employ in the present process comprise particularly the chloro and bromocyclopara'fiins which sometimes are also herein referred to as monochloro and monobromocycloalkanes. These halocycloalkanes thus contain only one halogen atom having anatomic weight between 35 and and a cycloparaffin ring, or a cycloparafiin ring with at least one attached alkyl group. Fluorocycloal- 3 kanes and iodocycloalkanes are also utilizable in this process.

Olefinic hydrocarbons utilizable in the present process include olefins and cycloolefins. Monoolefins may be either normally gaseous or normally liquid and comprise ethylene, propylene, butylenes, andalso normallyliquid olefins, the latter including various polymers of normally gaseous olefinic hydrocarbons. Aliphatic monoolefinic hydrocarbons which are utilizable in the present process may be obtained from any source and particularly from the products formed by catalytic and thermal cracking of oils, by dehydrogenation of paragtfinic hydrocarbons, or by dc! hydrating alcohols.

Cycloolefinic hydrocarbons utilizable in the present process comprise cyclic hydrocarbons of the general formula CnH2n-2 in which n represents an integer which is preferably at least 5. Cycloolefins containing five and six carbon atoms in the ring are preferred; that is, cyclopentene, alkyl cyclopentenes, cyclohexene, and alkyl cyclohexenes are the cycloolefins which I prefer to react with a halocycioparafiin- Thus a chlorocycloparaffin and a cycloolefin condense to form a chlorinated dicycloparaflin. Cyclopropene, cyclobutene, and alkylcyclobutenes are generally more difficult to obtain than the cycloolefins containing rings of 5 or 6 carbon atoms per molecule and accordingly are used less frequently in the present process.

Haloolefins which are condensed with saturated halides as herein set forth contain one double bond per molecule and at least one halogen atom, and comprise haloethenes, -propenes, -butenes, -pentenes, -hexenes, -heptenes, and higher molecular weight haloalkenes. Vinyl chloride, vinyl bromide, allyl chloride, allyl bromide, propenyl chloride, isopropenyl chloride, isocrotyl chloride, and methallyl chloride are representative of suitable haloolefins containing one halogen atom and one double bond per molecule and utilizable inthe present process. Polyhalomonoolefins include' such compounds as cis-dichloroethylene, 1,3-dichloropropene, trichloroethylenes, etc. The term haloolefins is used herein in reference to the above-mentioned unsaturated halogen compounds as well as to other unsaturated compounds such as halocycloolefins containing at least one halogen atom per molecule and a cycloolefin ring. The haloolefins preferred for use in this process contain chlorine or bromine but those containing fluorine or iodine are also suitable for condensation with a 'monohalocycloalkane;

Monohaloolefins may be formed in any suitable manner such as by the action of a halogen upon an olefin at a temperature at Which substitution occurs and substantially in excess of that at which the principal reaction is addition of halogen to the olefinic double bond. Monohaloolefins may also be prepared by the addition ofhalogen to an olefinic double bond to form a dihaloalkane from which one molecule of hydrogen halide may be removed by any of several well-known methods to produce a monohaloolefin. Furthermore, haloolefins may be prepared by addition of hydrogen halide to acetylenes.

"Halocycloolefins which may be employed in the present process include particularly monohalo cyclopentenes and monohalocyclohexenes. These halogenated compounds may be prepared by adding a halogen to a cycloolefin to form a dihalocycloparafiin and then eliminating: one molecule of hydrogen halide from said dihalocycloparaffin. Monohalocycloolefins may also be prepared by 4 splitting out the elements of water from a halohydrin as well as by other methods. Examples of suitable monohalocycloolefins include l-chlorol-cyclohexene, 1-ch1oro-3-cyclohexene, l-chlorolcyclopentene, 1 chloro-2-methyl-2-cyclopentene, etc.

Catalysts which are suitable for promoting the process of this invention comprise Friedel-Crafts metal halides including particularly ferric chloride, bismuth chloride, and zirconium chloride, zinc chloride, and the more reactive metal halides such as aluminum chloride and aluminum bromide.

These difierent catalytic materials containing metal'halides of the Friedel-Crafts type may be employed as such; they may be dissolved in a suitable solvent such at nitromethane, nitrobenzene, carbon disulfide, etc. Also complexes of Friedel-Crafts catalysts with organic compounds, and used catalyst sludges may be employed or the Friedel-Crafts halides may be composited with one another or supported on solid carriers or spacing materials to produce catalyst compositesof desired activities. Suitable catalyst carriers or supports include both adsorptive and substantially non-adsorptive materials, for example, alumina, activated clay, charcoal, crushed porcelain, raw and acid treated clays, diatomaceous earth, pumice, fire brick, etc. The carriers should be substantially inert in the sense that substantially no interaction which is detrimental to the activity or' selectivity of the catalyst composite occurs between the carrier and the metal halide.

In this process condensation of a monohalocycloalkane and a monoolefinic compound selected from the group consisting of a monoolefin and a halomonoolefin is somewhat analogous to the addition of a hydrogen halide to the double bond of an olefinic hydrocarbon. That is, the halocycloalkane apparently adds to the double bond of the unsaturated compound in this case produci'ng a halocycloalkane of higher molecular weight containing one ormore than one halogen atom.

For example, the condensation of l-chloro-imethylcyclohexane and propylene in the presence of bismuth chloride, which is a Friedel- Crafts catalyst, yields a chloropropyl-methylcyolohexane believed to be l-(p-chloropropybl-methylcyclohexane as illustrated by the following equation:

113o\ /c1 ing (g1 /o C\-CHz- H-CH3 H2O on, H2=CH-CH3) 1120' on; El on, H, (2112 V on; v o Other halonaphthenes or halocycloparafilns undergo similarcondensations with cycloolefins producing halogenated bicyclic hydrocarbons.

Similarly, the condensation of l-chloro-lmethyl-cyclopentane and vinyl chloride in the presence of bismuth chloride yields dichloroethylmethylcyclopentane or an isomer thereof as lllustrated by the following equation:

I |H2 n2o..o,Hi H20, e11.

Other halonaphthenes or halocycloparafiins also undergo condensation; with halocycloolefins producing halogenated bicyclic hydrocarbons.

CH1 CH; C HQO/ EH9 u an.

In some cases, as for example in the reaction of a halocyclohexane with ethylene, the primary product may react with a second molecule of ethylene thu yielding as the major product, a product having a molecular weight equal to the sum of the molecular Weight of the halonaphthene plus 't'wice'the molecular weight of the olefin. Thus, the reaction of bromocyclohexane with ethylene in the presence of aluminum chloride yields 1 (c-bromoethyl) 1 ethyl-cyclohexane.

Previous to my work, no condensation of a monohalocycloalkane with a monoolefin or halomonoolefin in the presence of a Friedel-Crafts halide catalyst has been reported. It was known, however, that a polyhaloalkane on which at least two halogen atoms (usually chlorine) are attached to the same primary (terminal) carbon atom could be condensed with a haloolefin. This reaction -is now very Well-known and is often referred to as the Prins reaction. The his tory of the Prins reaction is both interesting and significant. Prins published his first paper on the condensation reaction in 1910 (Boeseken and Prins, K. Akad. Wetenschappen, 19, 776 (1910); C. A., 5, 2843 (1911) It was shown that chloroform and carbon tetrachloride could be condensed with di-, in the presence of aluminum chloride as catalyst. Prins received German Patent 261,689 ,in 1913 and published additional papers on the subject in,

19l4 (J. Prakt. Chem., 89, 414 and 425 914)). In 1932 Prins renewed his interestin the reaction and made a very extensive study thereof. These papers were published in Rec. Trav. Chim. 51, 1065 (1932); 54, 249 (1935); V 56, 119 and 779 (1937); 57, 659 (1938). In none of these did he show that the condensation of a saturated monohalide (as a monohalocycloalkane) with an olefin or a haloolcfin is possible. On the contrary, he even stated that such a reaction is not possible and gave theoretical reasons to show Why it is not possible. In the meantime, other workers became inter sted in the Prins reaction and even obtained patent coverage on particular condensa tions. Thus, the Kirkbride Patent 2,298,564 is concerned with the condensation of carbon tetrachloride with dichloroethylene, the very condensation which Prins studied in 1910. Kirkbrides process differs from the reaction which was carried out more than 25 years earlier only in the fact that a higher temperature was used (I. e.,.

above 45 C. instead of at about 20 C.; Prins, however, did use temperatures above 4 C. with chloroform) which resulted in the formation of a chlorinated pentane instead of a chlorinated propane.- 1

Similarly, Sixt received Patent 2,068,772 relat-- ing to the condensation of 1,1-di-chloroethane with a chloroethylene, presumably because Prins was unable to bring about the con'densation with chloroethanes containing less than thre'e'chlorlne atoms (RectTrav. Chim. 56, 119 (1937.)).

-Haloalkanes .which were previously condensed tri-, and tetra-chloroethylene.

halides could not be with haloolefins are ethane.

to predict whether monoolefin. Indeed, sults, it is unexpected that a monohalocycloalkane can be condensed with an olefin or haloc 0 olefin.

If such a reaction is not unexpected, it is surprising that such a process was not claimed long ago in a patent or at least the chemical literature. I

In carryin out his reaction, Prins found he could reflux chloroform and dichloroethylene separately with aluminum chloride for a few? minutes and then combine the liquids and heat C. for two hours withthe'resultant formation of pentachloropropane (Rec. Travy It is important to-note them at 50 Chim, 54, 307 (1935)).

that the chloroform did with the catalyst. halides previously used are substances which can be treated with aluminum chloride without obtaining reaction. If a monohalocycloalkane such as those used in the reactions of this process not react when heated is contacted with aluminum chloride, (in the absence of the olefinic compounds of my process) at even room temperature, a very vigorous reaction occurs, hydrogen chloride is evolved and the resulting olefin polymerizes. In other words,

there is 'a vast difference between the polyhalo monohalocyclo-' alkanes used by Prins and the alkanes of the present process.

Another important difierence between the process of this invention and the prior art is the fact that the present process can be carried out in the presence of many Friedel-Crafts catalysts which range in activities from'such feebly active substances very active catalysts such as ferric chloride and aluminum chloride, whereas the prior art showed that only aluminum chloride could be used'as catalyst, for the condensation of a polyhaloal kane with a haloolefin, Prins having shown that not even so active a metal halide as ferric chlo ride will catalyze his there is a marked'difference in the chemical behavior of the monohalocycloalkanes of this process and the polyhaloalkanes of the prior art.

Furthermore, Prins himself did the reaction of the present fected; in 1932 he stated:

not believe that process could be cf benzene ring is not an addition to a double bond.

Prins, then, believed t hat saturated mono added to the ethylemc double bond. .It is also pertinent that he found that even chloroform could not be added to ethylene. Thus Prins stated When ethylene is led into a solution of aluminum chloride in chloroform or dichloromethane there is. formed, ac-

cording to my experiments, only'a trace of polymer whereas, as I have already shown, neither chloroform nor hexachloropropane added to ethylene. If, then, chloroform which reacts so readily with all; the chloroethylenes does not chloroform, carbon tetra: chloride, 1,1,di-chloroethane and 1,2,2-trichloro-;

described in Indeed, all of the saturated" as mercuric chloride and moderately active substances as bismuth chloride toreaction. Accordingly,

Alkyl halides (namely monohalides) require a much stronger activation the molecule is polarized" or activated by the'presence of a plurality 'of The difference in the ability of react with benzene (as opposed or halomonoole'finsf must :be' 'ex 2,481; redreact. with the ethylene; itself, there certainly: no basis for predicting. that. any". other: saturated chloride, as a monochlorocycloalltane", react-with: ethylene. and even less basis for expecting that amonohalide will; react. Accordingly; since chloroform which reactsso readily with all: the chloroethylenes doesnot reactwith ethylene itself it is not predictable that any other saturated halide such. as a monohalocyclm atkanewillz react; with; an, olefin. When a monochlorocycloalkane reacts, with: a monoolefin or. halomohoolefin, arr-unexpected result isobta'ined;

The mechanism of the; condensation of: an. olefin; with at chlorocycloparaffin is entirely differentfromtthatlof the condensation at an; olefin with. a; cycloparafiln. Thus the reaction of; .propylene; isopropylcyelohexane. From this. result; the ale kylation. ot the cyclohexane ring; might be. expeetedi upon: reacting propylene with. l-methyllechlorocyclohexane, asillustratedi by. the. equa-- tion-z:

However, the reaction or: l-methyld chlorm cyolohexane: with. propylene involves addition of the former to the double bond of the latter forming 1- (fl-chlorop'ropyl) -l methyicyclohex' Fromithe. above equations it is; apparent that the chlorine atom is involved in. the addition reaction, instead. of a nuclear hydrogen atom, whenreacting a-monochlorocycloalkane with an olefin as ethylene or propylene;

By my. process, it isv also; possible to condense secondary chlorocycloalkanes with. monoolefins andhalomonoolefins.- Thus the interaction of chlorocyclohexane with ethylene in the'presence of aluminum chloride gave of l-(B-chloroethyl) -l-ethyl-cyclohexaneand the analogous bromine; compound was; obtained from bromocyclohexane and ethylene in 32% yield; These results areanalogous to those obtained with tertiam chlorocycloalkanessuchv as l chloro-l methylcyclohexane.- These reactions are illus-'- with..methylcyc1ohexane yielded methylhigher.

C (32%- yield).

'fact that compound C may be converted by by dr'ogenation into 1,1-diethylcyclohexane which can be prepared by other means only'with extreme difficulty. H

The production of halo'cy'cloalkanes by my process is carried out-by reacting a halo'cycloal kane, and preferably a monohalocyc1oalkane,. witha monoolefin or halomonoolefin in the presence of a Friedel-C'rafts metal halide catalyst at a temperature-0ffrom about -30 to about 100 C.- The operating temperaturepreferred inorder to obtain, high yieldsof halocycloalkane condensation products isdepen-dent upon the particular catalyst and also upon the reactants.v Carefultemperature regulation within the. indicated range is essential only insofar as: the formationof the desired high yieldsis concerned.

When ferric chloride or aluminum chloride is. chosen. as. thecatalyst, the: operating tempera-- tures are from about -30. to about 50 C. but. preferred temperatures are from 10" to: C.-- If the: reaction is; carried out at: high tam. peratures in the range of aboutv to about 100 C., the: yields of halocycloalkane condensation products maybe lowbut at least some con denastion product will" be obtained; Aswill beevident from later examples, there was no careful temperature; control in the experiment of Example IV in which the temperature increased 4 gradually from l5-to +20 0., nor was there definitec'ontrol of temperature in-the experiment-- of Example VII' in which the reaction was so vigorous that the temperature of the reactionmixture was increased to about C. The'coh densationof Example VII could also be carriedoutby bubbling vinyl chloride'slowly through a well-stirred mixture ofchlorocyclohexane and aluminum chloride at any temperature between about 20 and +30 C; or even +F'"C'. or The yield of" diohlorocyclohexyletharie so obtained would be dependent upon the particu lar temperature usediri the. reaction, In general" good yields of condensation products are obtained" in this process atztemperatures in the mentioned" range and below about 50 C;

The condensation of a monohalocycloalk'ane. and an olefinic compound selected fromthe members of the group consisting of a monoolefi'nand' I: a.halomonoolefin inthe presence of a. catalyst as herein described may be carried out using.

,as' hydrogen chloride or hydrogen bromide:

Sometimes the introduction of hydrogento the reaction. mixture may have; a: beneficial efiectupon the reaction:

In batch type. operation, desired: proportions of: halocyoloalkahes; and monoolefin' or' halomonoan additional catalyst may comprise a halide.

olefin or mixtures containing these unsaturated compounds are introduced to a reactor containing the Friedel-Crafts catalyst; and the resultant commingled material is contacted until a substantial proportion of said reactants are converted into the desired halocycloalkane condensation product. The reaction mixture after separation from the catalyst is fractionally distilled or otherwise treated to separate unconverted halocycloalkane and unconverted olefinic compound from the higher boiling reaction products. The recovered unconverted material and used catalyst may be used in another run to produce quantity of the desired condensation product.

Continuous operation may be carried out by directing a halocycloalkane and an olefin or haloolefin through a reactor of suitable design containing catalyst or to which the catalyst is introduced continuously during the reaction. The

stationary bed of a granular composite containing a Friedel-Crafts metal In this type of treatment the operating conditions may be identical or they may diiTer somewhat from those operation. Thus when a mixture of halocycloalkane and a monoolefin or a halomonoolefin is passed through a reactor containing a catalyst,

for example, ferric chloride supported by granular porcelain, the formation of the desired halocycloalkane may be eifected by using a higher temperature and shorter time of treatment than those required for effecting similar conversion by contacting a similar reaction mixture and catalyst at a lower reactor such as an autoclave provided with a suitable stirring means. Used catalyst recovered from the process may be fortified by addition of fresh catalyst and may be returned to the condensation process for further use.

In some cases, it is advisable to commingle the charged halocycloalkane and unsaturated compound with a solvent such as a petroleum naphtha, for example, normal pentane, or a nitroparafiin, for example, nitromethane and then to eiiect the condensation in the presence of this added solvent. Obviously, the solvent chosen should be one which does not itself undergo undesirable reactions at the operating conditions employed.

Different halocycloalkanes produced by the present process may be used for various purposes. Such resultant monohalocycloalkanes may be utilized as solvents, they may be employed as intermediates in the synthesis of various organic compounds and for other purposes.

Polyhalocycloalkanes formed by this process are also valuable intermediates for the prepara tion of other useful compounds. The halocycloalkane-s having two halogen atoms attached to a terminal carbon atom may be readily hydrolyzed to form aldehydes with the same carbon structure by heating with water. Similarly, hydrolysis of dihalocycloalkanes in which two halogen atoms are attached to a non-terminal carbon atom yield ketones. The mentioned carbonyl compounds which may thus be produced from a di-halocycloalkane are useful as solvents or in the production of certain synthetic resins other products. The monohalocycloalkanes formed this process may be converted to alcohols or olefins by hydrolysis or dehydrogenation, respectively.

The following examples are given to illustrate employed in batch type temperature in a batch type 5 the character of results obtained in specific embodiments of this invention, although the data given are not introduced with the intention of restricting unduly the generally broad scope of the invention.

Example I 23 grams of l-chloro-l-methylcyclohexane boiling from 148 to 158 C., 10 grams of propylene, and 4 grams of bismuth chloride were sealed in an autoclave which was rotated at C. for four hours. The reaction product was then removed from the autoclave and separated into 26 grams of colorless liquid product and 4.5 grams of a brown catalyst layer. Distillation of the liquid product yielded (besides unreacted chloromethylcyclohexane) 4 grams of a substance boiling at 2l2-215 C. and having a refractive index, ri of 1.4700. These properties of this substance are those expected fora chloropropylmethylcyclohexane. It is believed that the substance which boiled at212215 C. was I-(B-chloropropyl) -1- methylcyclohexane.

Example II 15 grams of l chloro-l-methylcyclohexane and 3 grams of anhydrous ferric chloride were placed in a glass-lined steel autoclave to which ethylene was introduced to atmospheres pressure. The charged autoclave was theri rotated for four hours at 25 C. The resultant reaction product contained a 10% yield of l-(fi-chloro-ethyl) -1- methylcyclohexane.

Example III mitted to stand for about 15 hours at the same dex of 1.4634 at 20 C. This temperature. The reaction products were then removed from the autoclave and separated into 29 grams of dark brown liquid and a powdered black catalyst. Fractional distillation of the liquid yielded 6 grams of chloropropylmethylcyclopentane boiling at 55 to 57 C. under a pressure of 5 mm. of mercury and having a refractive inchloropropylmethylcyclopentane which had a normal boiling point of 188-l90 C. appeared to be l-(fi-chloropropyD- l-methylcyclopentane. I

Example IV A mixture of 33grams of l-chloro-l-methylcyclohexane and 16 grams of vinyl chloride in'a cylindrical glass reactor was cooled to 15 C. and 1 gram of anhydrous aluminum chloride was then added to the mixture after which the temperature increased gradually to +20 C. over a period of 15 minutes durin which the reactants were contacted with the catalyst. From the resultant reaction mixture there was obtained 20% of the theoretical yield of I-(Bp-diohloroethyhl-methylcyclohexane with a boiling point of 102 C. at a pressure of 12 mm. of mercury, an index of refraction, n of 1.4858, and a density of 1.07 at 20 C.

Example V In another run similar to that of Example IV a mixture of 16 grams of l-chloro-L-methy'lcyclopentane and 9.5 grams of vinyl chloride was (if anh drous the cooled reaction 'r'niiit'urfe in a rotatable steel ture of 3 grams or temperature was 30 eooledto -"'7"8"C.'in a grass cylinder "and "1 gram 'chloridewas added to which was shaken intermittently at atemperatureof from 10'to +5 C. for '7 minutes. At the end of this reac tion time the uppr'l'ayer bi reaction product was hem the "catalyst and distilled to give iii the theoretical yield of 1- (de-chloroethyDflihethylcycl'opefitane "which boiled between 1p 1 i Of mercury, had elretractive mdex, 'ng fl'of "1.4780, and a denany f 1108 'a't EmzmpleVI A mixture bf 50 grams of 'chlorocyclohexane and grams of vinyl chloride contained in a eylindrical "g-l'ass reactor was cooled to '-'?8 C. and 5 f'grams or "anhydrous -'-ferric chloride was mldde'd thereto. The-glass reactor was then'sealed autoclave, "nitrogen was intro'duced thereto to '50 atmospheres :pressure'and the charged autoclave was rotated at 25 C. for four hours. The autoclave was then permitted to stand for 16 hours at room temperature after "iwmeh the products wer'e'removed therefrom cono'f "7-4 :gmams or a mixture of brown liquid and id'lack *cata'lyst "sludge and 235 gi-ams "of con- 'd'ensible :gas. :After :being :separated from the catalyst, washed, and distilled, the liquid :prodirct wielded 5. 2 -cc.'-'o'if l,l-'dichloro 2-cy'clohexylethane which boiled at 205 sure and had a refractive index' of 124810 at 20 C. The amount of 1,1-dichloro-2-cyclohexylethane so obtained was equivalent to about 7% of thetheoretrcaiyieiueaised upon the quantit of P ehiorecyclehexahe charged to the reaction.

Example VII A cylindti'cal zglass reactor charged with 120 mms of chlorocyclol'rexane and 58-g-ram s -o1 viniyl chloride t lasco'ole'd43o-=70 '0. Then 5 grams "of "anhydrous aluminum chloride was added to the cooled=mixtureof chlorocyclohexahe an'd vin- .yl chloride and "the mixture, which was shaken intermittently, -increased in temperature from 90 to *"1-2" C." during *7 'nrinutes. The reaction was *so "vigorous that even-th'oi-igh --the glass reac- *tbr was immersed a cooling bath at "=-T8 (3., :the temperature -of the reaction mixture increased to about-e" (-3. during /2 minute. The reaction :mixture "was then maintained "at 30 C. for :15 minutes and then 'cooled to 0 C. during the next =155 minutes. After a total reaction time of ll-1 minutes, the -=reactionm-ixture was cooled to -40 C. and at that temperature -i grams of liquid products were decanted from 8 grams 4 of catalyst layer. The upper layer of the reaction spro'duet aifter washing and distilling yielded 60 gramsbf 1, 1 dichloro 2 -*cyclohexylethane which boiled 'at "87 to 88 C. at 'mrn'p'res'sure -'(-boiling "point calculated at 21 C. at 760 firm.) and had a "refractive index. n5 of 124810. The 60 -'g-rams of 1,-1 dichloro-2 cyclohexylethane represented about 35% "of the theoretical yield based upon the -quantity or chl'orocyclohexai're charged to "the reaction.

Example VIII Ethylene was bubbled through a stirred mixaluminum chloride and 31 grams of l-chloro-l-methylcyclohexan'edissolved in 41 grams of n-pentane diluent. The reaction to -25 C. A total of 15 grams of ethylene absorbed during one hour. The liquid upper layer was separated irom the 8 grams of orange-colored catalyst sludge, washed.

'12 erie'eanu distilled. Th'ere'vvas obtained 16'g'r'ams (43 of thetheoretic'ab of "1- fi-chloroet'hylfi 1- ni'ethylcyclohexane boiling at 62-6-6 at 3.5 mm.

mercury pressure. The product had a refractive index,-'n ,oT 1'Ai99 and a density, D4 OFOL'QO'ZH. Its molecular refraction was 4615; that "calculateffi'oi" Ci livcl'is lfikl.

Example Ethylene was "condensed with 'chlorocy'clohexane (5'0 ig' rams charged) in the presence "of '6 grams of aluniinum chloride at "-21 to -8 C. using the procedure described in Example Therewas ob'taihed'S "grams (10%) of thetheory of l-(fi-chloroethyl)-1-ethylcyc1ohei(ane, boiling :at JV-78 at -3 min. mercury pressure; its refracteame -11 was 1.4750.

Eitamble X The structure-of the product obtained in filxam- :ple- IX w-aseproved by showing that it was the same as that obtained-by condensing 'l-chloro-l-ethylcyclohexane (Sigrams) with ethylene in thepresence of aluminum chloride (3 grams) at about 16 to 0 (3., using the procedure described in Example VI-II.

Emample X-I Gondensation of hi'o'm'ocyclohei'he grams merged) withethylene (se-"ra'ms absoreem in the presence of 10 grams bi aluminum chloride at 20 10 C. using the procedure or E5;- ainple VIII ielded 6B egraiiis (32%) yield of 1- (e teem-awedethymycroheaafie, boiling at '%6 at 3 mm. "frier'c-ury pressure and having a re'fi active index, 'nof 124945 and a density, De, ='of 151 854. Its meiecmar'rr-racoon was 53.9 which is "identical with that calculated "for C1oH19Br. V

-Reduction 6f 'the bromide by treatment "with zinc and alcohol yielded 1,1=diethy1eye1'dhexan'e, a new hydrocarhoh, boili'ng at '17 3 "C. at atmos- 'phri'c erasure, no, 114501). This hydrocarbon be prepared enwwmnermeuuy, 1f at all, by "o'tli'e'rihethbds, thus illustrating on e 'ofthe useful resurcs obtainable via the products of "my invention.

Iclaiin'as my invention "1. A process for producing a higher boiling halocycloalkane which comprises chemically combining in the presence of a Friedel-Crafts h'a'l'icle c'atah' st "a mo'nohalocycloa/l'kane and a mon'o'olefinic co'ntponrid selected fromthemembe'i's'of the groupconsistin'g of a monoolefin an'd'a halomonoolefin.

2. -'A process for producing, a higher boiling halocycloalkane which'cdmprises chemically combining in the presence of a 'Friedel-Crafts metal halide 'catalyst a in'onochlorocycloalkane and a moi-ioolefinic compound selected from the membe'rso'f the group consistin'goi "a monoolefin and a halomonoolefin.

3. A process which'cornprises reacting a monohalocycloa-lkane and a monoolefinic compound selected from the "members of the group consisting of a monoolefin and a halomonoolefin at condensing conditions in the presence of a Eriedel-Grafts metal halide catalyst to form a higher boiling halocycloalkane having a molecular weight equal to the sum of the molecular weights of the --reactants, and recovering said higher boiling halocycloalkane.

A process which comprises reacting a monohalbeycieaikahe and a monoolefin at condensing conditions in the presence of a Friedel-Crafts (5 tem halide catalyst to form a monohalocyclo- 13 alkane having a molecular weight equal to the sum of the molecular weights of the reactants, and recovering said last named monohalocycloalkane.

5. A process which comprises reacting a monohalocycloalkane and a halomonoolefin at condensing conditions in the presence of a Friedel- Crafts metal halide catalyst to form a polyhalocycloalkane having a molecular weight equal to the sum of the molecular weights of the reactants, and recovering said polyhalocycloalkane.

6. A process which comprises reacting a monohalocycloalkane and a monoolefin at a temperature of from about 30" to about 100 C. in the presence of a Friedel-Crafts metal halide catalyst to form a higher boiling monohalocycloalkane having a molecular Weight equal to the sum of the molecular weights of the reactants and recovering said higher boiling halocycloalkane.

7. A process which comprises reacting a monohalocycloalkane and a halomonoolefin at a temperature of from about 30 to about 100 C. in the presence of a Friedel-Crafts metal halide catalyst to form a polyhalocycloalkane having a molecular weight equal to the sum of the molecular weights of the reactants, and recovering said polyhalocycloalkane.

8. A process which comprises reacting a monochlorocycloalkane and a monoolefin at a tempera ture of from about 30 to about 100 C. in the presence of a Friedel-Crafts metal halide catalyst to form a higher boiling monochlorocycloalkane having a molecular weight equal to the sum of the molecular weights of the reactants, and recovering said higher boiling monochlorocycloalkane.

9. A process which comprises reacting a monobromocycloalkane and a monoolefin at a temperature of from about 30 to about 100 C. in the presence of a Friedel-Crafts metal halide catalyst to form a higher boiling monobromocycloalkane having a molecular weight equal to the sum of the molecular weights of the reactants, and recovering said higher boiling monobromocycloal kane.

10. A process which comprises reacting a monochlorocycloalkane and a monochloroolefin at a temperature of from about 30 to about 100 C. in the presence of a Friedel-Crafts metal halide catalyst to form a dichlorocycloalkane having a molecular weight equal to the sum of the molecular weights of the reactants, and recovering said dichlorocycloalkane.

11. A process which comprises reacting a monobromocycloalkane and a monobromoolefin at a temperature of from about 30 to about 100 C. in the presence of a Friedel-Crafts metal halide catalyst to form a dibromocycloalkane having a molecular weight equal to the sum of the molecular weights of the reactants, and recovering said dibromocycloalkane.

12. A process for producing a higher boiling halocycloalkane which comprises reacting a tertiary monohalocycloalkane and a monoolefinic compound selected from the members of the group consisting of a monoolefin and a halomonoolefin at a temperature of from about 30 to about 100 C. in the presence of a Friedel- Crafts metal halide catalyst, and recovering the resultant halocycloalkane.

13. A process for producing a higher boiling halocycloalkane which comprises reacting a secondary monohalocycloalkane and a monoolefinic compound selected from the members of the group consisting of a monoolefin and a halo- 14 monoolefin at a temperature of from about 30 to about C. in the presence of a Friedel- Crafts metal halide catalyst, and recovering the resultant halocycloalkane.

14. The process defined in claim 12 further characterized in that chlorine is the halogen of said halocycloalkanes and halomonoolefin.

15. The process defined in claim 13 further characterized in that chlorine is the halogen of said halocycloalkanes and halomonoolefin.

16. A process for producing l-(B-chloroethyD- l-methylcyclohexane which comprises reacting 1-=chloro-l-methylcyclohexane and ethylene in the presence of a ferric chloride catalyst at a temperature of from about 30 to about 50 C., and recovering the resultant l-(p-chloroethylll-methylcyclohexane.

17. A process for producin l-(fl-chloropropyl)1-methylcyclopentane which comprises reacting l chloro-l-methylcyclopentane and propylene in the presence of a ferric chloride catalyst at a temperature of from about 30 to about 50 C., and recovering the resultant l-(fichloroproyl) -1,-methylcyclopentane.

18. A process for producing l-(p c-dichloroethyl) -1-methylcyclohexane which comprises reacting l-chloro-l-methylcyclohexane and vinyl chloride in the presence of an aluminum chloride catalyst at a temperature of from about 30 to about 50 C., and recovering the resultant 1-(fl,B-dich1or0ethy1) 1 methylcyclohexane.

19. A process for producing l-(p-chloroethyl) l-ethylcyclohexane which comprises reacting chlorocyclohexane and ethylene in the presence of an aluminum chloride catalyst at a temperature of from about 30 to about 50 C., and recovering the resultant l-(B-chloroethyl) -1-ethylcyclohexane.

20. A process for producing 1-(,8-bromoethyl)- l-ethylcyclohexane which comprises reacting bromocyclohexane and ethylene in the presence of an aluminum chloride catalyst at a temperature of from about 30 to about 50 C., and recovering the resultant l-(fi-bromoethyl)1-ethylcyclohexane.

21. A process which comprises reacting a tertiary monochlorocyclo-alkane with a chloromono-olefin in the presence of a Friedel-Crafts metal halide catalyst at a temperature of from about 20 C. to about +100 C. to form a polychlorocycloalkane having a molecular weight equal to the sum of the molecular weights of said monochlorocyclo-alkane and said chloromono-olefin, and recovering said polychlorocycloalkane from the resultant products.

22. A process which comprises reacting a tertiary monochlorocyclo-alkane with a monochloromono-olefin in the presence of a Friedel- Crafts metal halide catalyst at a temperature of from about 20 C. to about +50 C. to form a dichlorocyclo-alkane having a molecular weight equal to the sum of the molecular weights of said monochlorocyclo-alkane and said monochloromono-olefin, and recovering said dichlorocycloalkane from th resultant products.

LOUIS SCHMERL'ING.

REFERENCES CITED UNITED STATES PATENTS ame Date Number N Schmerling Jan. 13, 1948 

